Apparatus and method to achieve continuous interface and ultrathin film during atomic layer deposition

ABSTRACT

A method and apparatus for performing atomic layer deposition in which a surface of a substrate is pretreated to make the surface of the substrate reactive for performing atomic layer deposition.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is a divisional of U.S. patent application Ser.No. 09/470,279, filed Dec. 22, 1999 entitled “Apparatus and Method toAchieve Continuous Interface and Ultrathin Film During Atomic LayerDeposition.”

[0002] The United States Government has rights in this inventionpursuant to Contract No. F33615-99-C-2961 between Genus, Inc. and theU.S. Air Force Research Laboratory.

BACKGROUND OF THE INVENTION

[0003] The present invention relates generally to semiconductortechnology and, more particularly, to a method and apparatus for thepractice of atomic layer deposition.

[0004] In the manufacture of integrated circuits, many methods are knownfor depositing and forming various layers on a substrate. Chemical vapordeposition (CVD) and its variant processes are utilized to deposit thinfilms of uniform and, often times conformal coatings over high-aspectand uneven features present on a wafer. However, as device geometriesshrink and component densities increase on a wafer, new processes areneeded to deposit ultrathin film layers on a wafer. The standard CVDtechniques have difficulty meeting the uniformity and conformityrequirements for much thinner films.

[0005] One variant of CVD to deposit thinner layers is a process knownas atomic layer deposition (ALD). ALD has its roots originally in atomiclayer epitaxy, which is described in U.S. Pat. Nos. 4,058,430 and4,413,022 and in an article titled “Atomic Layer Epitaxy” by Goodman etal.; J. Appl. Phys. 60(3), Aug. 1, 1986; pp. R65-R80. Generally, ALD isa process wherein conventional CVD processes are divided intosingle-monolayer depositions, wherein each separate deposition steptheoretically reaches saturation at a single molecular or atomicmonolayer thickness or less and, then, self-terminates.

[0006] The deposition is an outcome of chemical reactions betweenreactive molecular precursors and the substrate (either the basesubstrate or layers formed on the base substrate). The elementscomprising the film are delivered as molecular precursors. The desirednet reaction is to deposit a pure film and eliminate “extra” atoms(molecules) that comprise the molecular precursors (ligands). In astandard CVD process, the precursors are fed simultaneously into thereactor. In an ALD process, the precursors are introduced into thereactor separately, typically by alternating the flow, so that only oneprecursor at a time is introduced into the reactor. For example, thefirst precursor could be a metal precursor containing a metal element M,which is bonded to an atomic or molecular ligand L to form a volatilemolecule ML_(x). The metal precursor reacts with the substrate todeposit a monolayer of the metal M with its passivating ligand. Thechamber is purged and, then, followed by an introduction of a secondprecursor. The second precursor is introduced to restore the surfacereactivity towards the metal precursor for depositing the next layer ofmetal. Thus, ALD allows for single layer growth per cycle, so that muchtighter thickness controls can be exercised over standard CVD process.The tighter controls allow for ultrathin films to be grown.

[0007] In practicing CVD, a nucleation step is assumed when a film ofstable material is deposited on a stable substrate. Nucleation is anoutcome of only partial bonding between the substrate and the film beingdeposited. Molecular precursors of CVD processes attach to the surfaceby a direct surface reaction with a reactive site or by CVD reactionbetween the reactive ingredients on the surface. Of the two, the CVDreaction between the reactive ingredients is more prevalent, since theingredients have much higher affinity for attachment to each other. Onlya small fraction of the initial film growth is due to direct surfacereaction.

[0008] An example of nucleation is illustrated in FIGS. 1-3. FIG. 1shows a substrate 10 having bonding locations 11 on a surface of thesubstrate. Assuming that the CVD reaction involves a metal (M) and aligand (L_(x)) reacting with a non-metal (A) and hydrogen (H_(z)), theadsorbed species diffuse on the surface and react upon successfulML_(x)-AH_(z) collisions. However, the reaction does not occur at all ofthe potential attachment (or bonding) locations 11. Generally, defectsites (sites having irregular topology or impurity) are likely to trapmolecular precursors for extended times and, therefore, have higherprobability to initiate nucleation. In any event, as shown in FIG. 1,the bonding of the precursor to the surface occurs at only some of thebonding locations 12.

[0009] Subsequently, as shown in FIG. 2, the initial bonding sites 12commence to further grow the thin film material on the surface of thesubstrate 10. The initial reaction products on the surface are thenucleation seed, since the attached products are immobile and diffusingmolecular precursors have a high probability to collide with them andreact. The process results in the growing of islands 13 on the substratesurface together with the continuous process of creating new nucleationsites 14. However, as the islands 13 grow larger, the formation of newnucleation seeds is suppressed because most of the collisions occur atthe large boundaries of the islands 13.

[0010] As the islands 13 enlarge three-dimensionally, most of theadsorption and reaction processes occur on the island surfaces,especially along the upper surface area of the islands 13. Eventually,this vertical growth results in the islands becoming grains. When thegrains finally coalesce into a continuous film, the thickness could beon the order of 50 angstroms. However, as shown in FIG. 3, the separatednucleation sites can result in the formation of grain boundaries andvoids 15 along the surface of the substrate, where potential bondingsites failed to effect a bond with the precursor(s). The grainboundaries and voids 15 leave bonding gaps along the surface of thesubstrate so that substantial film height will need to be reached beforea continuous upper surface of the film layer is formed.

[0011] Although the results described above from nucleation is a problemwith the standard CVD process, the effect is amplified with ALD. SinceALD utilizes one precursor at a time, the initial bonding will occur dueto surface reaction of the initial precursor with sparse surfacedefects. Accordingly, seed nucleation sites 12 are very sparse (moresparse than CVD) and nucleation proceeds by growing ALD layers on thesefew seed sites. As a result, the nuclei grow three-dimensional islands13 and coalesce only at thickness that are comparable to the distancebetween the nucleation seeds. That is, the voids 15 could be much largerin size, so that a much higher structure is needed to provide acontinuos upper surface for the film when only ALD is used.

[0012] Accordingly, if an ALD film can initiate growth on a substratepredominantly by nucleation, the film grows discontinuously for a muchthicker distance. Ultimately a much thicker film is practically neededin the case of ALD to achieve continuous film, than that which can beobtained from CVD processes.

[0013] The present invention is directed to providing a technique todeposit ALD thin films of reduced thickness that has continuousinterface and film.

SUMMARY OF THE INVENTION

[0014] A method and apparatus for performing atomic layer deposition inwhich a surface of a substrate is pretreated to make the surface of thesubstrate reactive for performing atomic layer deposition (ALD). As aresult, the ALD process can start continuously without nucleation orincubation, so that continuous interfaces and ultrathin films areformed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015]FIG. 1 is a cross-sectional diagram showing a problem encounteredwith prior art CVD processes, in which sparse seed nuclei are formed toinitiate film growth by non-continuous nucleation.

[0016]FIG. 2 is a cross-sectional diagram showing the start ofnucleation emanating from the chemical attachment shown in FIG. 1, inwhich the spacing between the nucleation sites results in the formationof separated islands as the deposition process progresses.

[0017]FIG. 3 is a cross-sectional diagram showing the result of furthergrowth of the deposited layer of FIG. 2, in which the formation of grainboundaries and voids requires more than desirable thickness to bedeposited to obtain a continuous layer at the surface.

[0018]FIG. 4 is a cross-sectional diagram showing an embodiment of thepresent invention in pretreating a surface of a substrate to activatethe surface, prior to performing atomic layer deposition to grow anultra thin film layer.

[0019]FIG. 5 is a cross-sectional diagram showing the presence of manymore active sites on the surface of the substrate after surfacepretreatment shown in FIG. 4 is performed.

[0020]FIG. 6 is a cross-sectional diagram showing a first sequence forperforming ALD when a first precursor is introduced to the preparedsurface of FIG. 5.

[0021]FIG. 7 is a cross-sectional diagram showing a formation of ligandson the substrate surface of FIG. 6 after the first precursor reacts withthe pretreated surface and the subsequent introduction of a secondprecursor.

[0022]FIG. 8 is a cross-sectional diagram showing the restoration of thesubstrate surface of FIG. 7 so that the first precursor can bereintroduced to repeat the ALD cycle for film growth and, in addition, acontinuous interface layer of the desired film is deposited on thesubstrate by the sequences of FIGS. 5-7.

[0023]FIG. 9 is a cross-sectional diagram showing a formation of a nextALD monolayer atop the first monolayer shown in FIG. 8 to further growthe layer above the substrate one atomic/molecular layer at a time.

[0024]FIG. 10 is a cross-sectional diagram showing an alternativepretreatment technique in which an intermediate layer is formed toprovide activation sites on the surface of the substrate prior toperforming ALD.

[0025]FIG. 11 is a block diagram showing one reactor apparatus forperforming ALD, as well as pretreating the surface by practicing thepresent invention.

DETAILED DESCRIPTION OF THE INVENTION

[0026] The practice of atomic layer deposition (ALD) to deposit a filmlayer onto a substrate, such as a semiconductor wafer, requiresseparately introducing molecular precursors into a processing reactor.The ALD technique will deposit an ultrathin film layer atop thesubstrate. The term substrate is used herein to indicate either a basesubstrate or a material layer formed on a base substrate, such as asilicon substrate. The growth of the ALD layer follows the chemistriesassociated with chemical vapor deposition (CVD), but the precursors areintroduced separately.

[0027] In an example ALD process for practicing the present invention,the first precursor introduced is a metal precursor comprising a metalelement M bonded to atomic or molecular ligand L to make a volatilemolecule ML_(x) (the x, y and z subscripts are utilized herein to denoteintegers 1, 2, 3, etc.). It is desirable that the ML_(x) molecule bondwith a ligand attached to the surface of the substrate. An exampleligand is a hydrogen-containing ligand, such as AH, where A is anonmetal element bonded to hydrogen. Thus, the desired reaction is notedas AH+ML_(x)→AML_(y)+HL, where HL is the exchange reaction by-product.

[0028] However, in a typical situation as noted in the Backgroundsection above, the substrate surface does not possess ample bondingsites for all the potential locations on the surface. Accordingly, theML_(x) precursor bonding to the surface can result in the formation ofislands and grains which are sufficiently far apart to cause theproblems noted above. In order to grow continuous interfaces and films,the present invention is practiced to pretreat the surface of thesubstrate prior to ALD in order to have the surface more susceptible toALD. In the preferred embodiment the substrate surface is first treatedto make the surface more reactive. This is achieved by forming reactivetermination on the surface which will then react with the first ALDprecursor.

[0029]FIG. 4 shows one embodiment for practicing the present invention.In FIG. 4, a substrate 20 (again, substrate is used herein to refer toeither a base substrate or a material layer formed on a base substrate)is shown upon which ALD is performed. Instead of applying the ML_(x)precursor initially onto the substrate 20, one or more radicalspecie(s), including such species as oxygen, hydrogen, OH, NH₂, Cl andF, is introduced to react with a surface 21 of the substrate 20. Thespecies can be remote plasma generated and carried to the processingchamber. The reactive species can be selected to react with mostsurfaces, however, the particular specie selected will depend on thesurface chemistry. A given specie is utilized to modify the surface 21.The reactive specie typically will modify the surface by exchangingother surface species and/or attaching to previously reconstructedsites.

[0030] For example, SiO₂ surface with approximately 100% siloxane SiOSibridge is generally inert. OH, H or O radical exposure can efficientlyinsert HOH into the SiOSi to generate 2 Si—OH surface species that arehighly reactive with ML_(x) molecular precursor. In FIG. 4, a genericAH_(z) reaction is shown to treat the surface 21 of the substrate 20. Anumber of example reactions using a particular species to treat varioussurfaces is described later below.

[0031] The introduction of the pretreatment plasma into the processingchamber containing the substrate 20 results in the formation of surfacespecies at various desired bonding sites. Thus, as shown in FIG. 5, thesurface is shown containing AH sites. It is desirable to have the AHspecies at many of the potential bonding sites. Subsequently, as shownin FIG. 6, the first precursor ML_(x) is introduced to start the ALDprocess for growing a film layer having the composition MA.

[0032] It should be noted that the prior art practice of performing ALDcommences by the introduction of ML_(x). Since the prior art does notpretreat the surface 21, there is a tendency for the surface to have lotless potential bonding sites. That is, there are lot less AH sites onnon-treated surfaces versus the number available for the pretreatedsurface 21 shown in FIG. 6. Accordingly, with less bonding sites on thesurface, the earlier described problems associated with nucleation canoccur. However, the pretreated surface 21 allows for many more bondingsites to be present on the surface to reduce the above-noted problem.

[0033] FIGS. 7-9 show the remaining sequence for performing ALD. Afterthe ML_(x) precursor is introduced, the AH+ML_(x)→AML_(y)+HL reactionoccurs, wherein HL is exchanged as the reaction by-product. As shown inFIG. 7, the surface of the substrate 21 now contains the MA-Lcombination, which then reacts with the second precursor comprisingAH_(z). The second precursor, shown here comprising a nonmetal element Aand hydrogen reacts with the L terminated sites on the surface 21. Thehydrogen component is typically represented by H₂O, NH₃ or H₂S. Thereaction ML+AH_(z)→MAH+HL results in the desired additional element Abeing deposited as AH terminated sites and the ligand L is eliminated asa volatile by-product HL. The surface 21 now has AH terminated sites, asshown in FIG. 8.

[0034] At this point of the process, the first precursor has beenintroduced and deposited by ALD, followed by the second precursor, alsoby ALD. The sequence of surface reactions restores the surface 21 to theinitial condition prior to the ML_(x) deposition, thereby completing theALD deposition cycle. Since each ALD deposition step is self-saturating,each reaction only proceeds until the surface sites are consumed.Therefore, ALD allows films to be layered down in equal meteredsequences that are identical in chemical kinematics, deposition percycle, composition and thickness. Self-saturating surface reactions makeALD insensitive to transport non-uniformity either from flow engineeringor surface topography, which is not the case with other CVD techniques.With the other CVD techniques, non-uniform flux can result in differentcompletion time at different areas, resulting in non-uniformity ornon-conformity. ALD, due to its monolayer limiting reaction, can provideimproved uniformity and/or conformity over other CVD techniques.

[0035]FIG. 9 illustrates the result of a subsequent ALD formation of theMA layer when the next ML_(x) sequence is performed to the surface ofthe substrate shown in FIG. 8. Thus, additional ALD deposition cycleswill further grow the film layer 22 on the surface 21, one atomic ormolecular layer at a time, until a desired thickness is reached. Withthe pretreatment of the surface 21, nucleation problems noted earlierare inhibited, due to ample bonding sites on the surface. Thus, theinitial ALD layers, as well as subsequent ALD layers, will have amplebonding sites on the surface to attach the reactive species. Continuousultrathin film layers of 50 angstroms and under can be deposited withacceptable uniformity and conformity properties when practicing thepresent invention.

[0036] It is appreciated that the pretreatment of the surface 21 can beachieved to deposit enough radical species to exchange with the surface.In this instance, these radical species (shown as AH in the exampleillustrated) provide termination sites for bonding to the ML_(x)precursor. However, in some instances, it may be desirable to actuallydeposit an intermediate layer above the surface 21. In this instance, anactual intermediate layer 23 is formed above the surface 21 and in whichthe termination sites are actually present on this layer 23. This isillustrated in FIG. 10. Again, this layer can be deposited by a plasmaprocess, including ALD. Then, the ALD process sequence, commencing withthe deposition of ML_(x) can commence.

[0037] An intermediate layer may be required in some instances when thesubstrate cannot be made reactive with either of the ALD molecularprecursors by a simple attachment or exchange of surface species. Theultra thin intermediate layer 23 is deposited as part of thepretreatment process. The intermediate layer 23 provides a new surfacethat is reactive to one or both precursors. The layer 23 is formedhaving a thickness which is kept minimal, but sufficient for activation.The intermediate layer 23 may be conductive, semiconductive orinsulating (dielectric). Typically, it will match the electricalproperties of either the substrate 20 or the overlying film being grown.For example, layer 23 is needed as a transition layer when W or WN_(x)films are deposited on SiO₂. In this instance, Al₂O₃ (which is aninsulator) or TiN, Ti, Ta or Ta_(x)N (which are conductors) can be usedfor the intermediate layer 23.

[0038] It is to be noted further, that the intermediate layer 23 can bedeposited by ALD for the pretreatment of the surface. Additionally, thesurface 21 of the substrate 20 can be pretreated first by the firstmethod described above to prepare the surface 21 for the deposition ofthe intermediate layer 23. Although this does require additionalprocess, it may be desirable in some instances.

[0039] It is appreciated that the pretreatment of surface 21 is achievedby a plasma process in the above description, including the use of ALD.However, other techniques can be used instead of a plasma process topretreat the surface 21. Thus, the surface 21 can be treated, even theintermediate layer 23 grown, by other techniques. Furthermore, aleaching process can be utilized. Since some surfaces are quite inert, aprocess other than reactive exchange or attachment may be desirable. Forexample, hydrocarbon and fluorocarbon polymers are utilized for low-kdielectrics. Adhesion of films, for sealing (insulating) or for forminga barrier (metals, metal nitrides), is difficult to achieve. In theseinstances, leaching hydrogen or fluorine from the top layer of thepolymer can activate the surface for ALD.

[0040] Thus, a number of techniques are available for pretreating asurface of a substrate so that the surface is more active for ALD. Thepresent invention can be implemented in practice by a number ofchemistries and chemical reactions. A number of examples are providedbelow with relevant equations. It is to be understood that the exampleslisted below are provided as examples and in no way limit the inventionto just these examples.

EXAMPLE 1 ALD Deposition of Al₂O₃ on Silicon

[0041] A silicon substrate is first activated (pretreated) by formingthin layers of silicon oxide (SiO₂) or silicon oxinitride, in which OHand/or NH_(x) groups form the terminations. The process involvesO₂/H₂/H₂O/NH₃ remote plasma that includes different ratios of theconstituents to form the terminations prior to the introduction of thefirst precursor to grow the Al₂O₃ thin film layer on silicon.

Si—H+OH.+H.+NH_(x).→Si—OH+Si—NH_(x)

[0042] (where “.” defines a radical)

Si—OH+Al(CH₃)₃→Si—O—Al(CH₃)₂+CH₄

Si—NH_(x)+Al(CH₃)₃→Si—NH_(x−1)—Al(CH₃)₂+CH₄

EXAMPLE 2 ALD Deposition of Al₂O₃ on Silicon

[0043] The silicon substrate is activated by forming thin layers of SiO₂that is hydroxilated by exposing HF cleaned (H terminated) silicon to apulse of H₂O at temperatures below 430° C. This process results in aself-saturated layer of SiO₂ that is approximately 5 angstroms thick.

Si—H+H₂O→Si—O—Si—OH+H₂

Si—OH+Al(CH₃)₃→Si—O—Al(CH₃)₂+CH₄

EXAMPLE 3 ALD Deposition of Al₂O₃ on WN_(x)

[0044] NH₃/H₂/N₂ plasma is used to leach fluorine from the top layers ofthe WN_(x) film and terminate the surface with NH_(x) species. Thesespecies are reacted with trimethyl aluminum (TMA) to initiate depositionof Al₂O₃ on WN_(x).

W_(x)N+H.+NH_(x)→W—NH_(x)

W—NH_(x)+Al(CH₃)₃→W—NH_(x−1)—Al(CH₃)₂+CH₄

EXAMPLE 4 ALD Deposition of Al₂O₃ on TiN

[0045] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species. These species are reacted with TMA to initiate Al₂O₃ ALD.

TiN+He.+NH_(x).→Ti—NH_(x)

TiNH_(x)+Al(CH₃)₃TiNH_(x−1)—Al(CH₃)₂+CH₄

EXAMPLE 5 ALD Deposition of Al₂O₃ on Ti

[0046] NH₃/H₂/N₂ plasma is used to nitridize the surface and terminatethe surface with NH_(x) species. Maintain conditions to avoid extensivenitridization into the Ti film. The NH_(x) species are reacted with TMAto initiate Al₂O₃ ALD.

Ti+NH_(x).+H.→TiNH_(x)

TiNH_(x)+Al(CH₃)₃→TiNH_(x−1)—Al(CH₃)₂+CH₄

[0047] EXAMPLE 6

ALD Deposition of Al₂O₃ on W

[0048] NH₃/H₂/N₂ plasma is used to nitridize the surface and terminatethe surface with NH_(x) species. Maintain conditions to avoid extensivenitridization into the W film. The NH_(x) species are reacted with TMAto initiate Al₂O₃ ALD.

W+NH_(x).+H.→WNH_(x)

W—NH_(x)+Al(CH₃)₃→W—NH_(x−1)—Al(CH₃)₂+CH₄

EXAMPLE 7 ALD Deposition of Al₂O₃ on Ta

[0049] NH₃/H₂/N₂ plasma is used to nitridize the surface and terminatethe surface with NH_(x) species. Maintain conditions to avoid extensivenitridization into the Ta film. The NH_(x) species are reacted with TMAto initiate Al₂O₃ ALD.

Ta+NH_(x).+H.→TaNH_(x)

TaNH_(x)+Al(CH₃)₃→TaNH_(x−1)—Al(CH₃)₂+CH₄

EXAMPLE 8 ALD Deposition of Al₂O₃ on Ta_(x)N

[0050] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species. The NH_(x) species are reacted with TMA to initiate Al₂O₃ ALD.

Ta_(x)N+NH_(x).+H.→TaNH_(x)

TaNH_(x)+Al(CH₃)₃→TaNH_(x−1)—Al(CH₃)₂ 30 CH₄

EXAMPLE 9 ALD Deposition of Ta₂O₅ on Al₂O₃

[0051] The process involves O₂/H₂/H₂O remote plasma that includesdifferent ratios of the constituents. This plasma is used to terminatethe surface with OH species that are reactive with TaCl₅.

Al₂O₃+OH.+O.+H.→Al₂O₃—OH

Al₂O₃—OH+TaCl₅→Al₂O₃—O—TaCl₄+HCl

EQUATION 10 ALD Deposition of Al_(2O) ₃ on Ta₂O₅

[0052] The process involves O₂/H₂/H₂O remote plasma that includesdifferent ratios of the constituents. This plasma is used to terminatethe surface with OH species that are reactive with TaCl₅.

Ta₂O₅+O.+H.+OH.→Ta₂O₅—OH

Ta₂O₅—OH+Al(CH₃)₃→Ta₂O₅—O—Al(CH₃)₂+CH₄

EXAMPLE 11 ALD Deposition of TiO_(x) on Al₂O₃

[0053] The process involves O₂/H₂/H₂O remote plasma that includesdifferent ratios of the constituents. This plasma is used to terminatethe surface with OH species that are reactive with TMA.

Al₂O₃+O.+H.+OH.→Al₂O₃—OH

Al₂O₃—OH+TiCl₄→Al₂O₃—O—TiCl₃+HCl

EXAMPLE 12 ALD Deposition of Al₂O₃ on TiO_(x)

[0054] The process involves O₂/H₂/H₂O remote plasma that includesdifferent ratios of the constituents. This plasma is used to terminatethe surface with OH species that are reactive with TiCl₄.

TiO₂+O.+H.+OH.→TiO₂—OH

TiO₂—OH+Al(CH₃)₃→TiO₂—O—Al(CH₃)₂+CH₄

EXAMPLE 13 ALD Deposition of TiO_(x) on TiN

[0055] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species. The NH_(x) species are reacted with TiCl₄ to initiate TiO_(x)ALD.

TiN+H.+NH_(x).→Ti—NH_(x)

Ti—NH_(x)+TiCl₄→TiNH_(x−1)TiCL₃+HCl

EXAMPLE 14 ALD Deposition of W on TiN

[0056] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species. The NH_(x) species are reacted with TiCl₄ to initiate TiN ALD.

TiN+H.+NH_(x).→Ti—NH_(x)

Ti—NH_(x)+WF₆→TiNH_(x−1)—WF₅+HF

EXAMPLE 15 ALD Deposition of WN_(x) on TiN

[0057] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species. The NH_(x) species are reacted with TiCl₄ to initiate WN_(x)ALD.

TiN+H.+NH_(x).→Ti—NH_(x)

Ti—NH_(x)+WF₆→TiNH_(x−1)—WF₅+HF

EXAMPLE 16

[0058] ALD Deposition of WN_(x) on SiO₂

[0059] O₂/H₂/H₂O remote plasma that includes different ratios of theconstituents is used to terminate the surface with OH species that arereactive with TiCl₄. The TiCl₄ species is used to grow an intermediatelayer of Ti or TiN. The final layer is terminated with NH_(x) species(from the TiN ALD) which reacts with WF₆ to initiate the WN_(x) ALDprocess.

SiO₂+H.+O.+OH.→Si—OH

Si—OH+TiCl₄→SiO—TiCl₃+HCl

SiO—TiCl₃+NH₃→SiO—TiN—NH_(x)+HCl

SiO—TiN—NH_(x)+WF₆→SiO—TiN—NH_(x−1)WF₅+HF

EXAMPLE 17 ALD Deposition of W on SiO₂

[0060] O₂/H₂/H₂O remote plasma that includes different ratios of theconstituents is used to terminate the surface with OH species that arereactive with TiCl₄. The TiCl₄ species is used to grow an intermediatelayer of Ti or TiN. The final layer is terminated with NH_(x) species(from the TiN ALD) which reacts with WF₆ to initiate the W ALD process.

SiO₂+H.+O.+OH.→Si—OH

Si—OH+TiCl₄→SiO—TiCl₃+HCl

SiO—TiCl₃+NH₃→SiO—TiN—NH_(x)+HCl

SiO—TiN—NH_(x)+WF₆→SiO—TiN—NH_(x−1)WF₅ +HF

[0061] Alternatively, TaCl₅ can be used for growing an intermediateTa_(x)N layer.

EXAMPLE 18 ALD Deposition of WN_(x) on Hydrocarbon Polymer (Low-kDielectric Layer)

[0062] NF₃ remote plasma generates fluorine atoms that leach outhydrogen from the hydrocarbon. The leached surface is reacted with TiCl₄and followed by TiN or Ti/TiN ALD of a thin intermediate layer. TheNH_(x) terminated surface that is prepared during the TiN ALD is reactedwith WF₆ to initiate WN_(x) ALD.

C_(n)H_(m)+F.→C_(p)H_(q)C.

C_(p)H_(q)C.+TiCl₄→C_(p)H_(q−1)CTiCl₃+HCl

C_(p)H_(q−1)CTiCl₃+NH₃→C_(p)H_(q−1)CtiN—NH_(x)+HC

C_(p)H_(q−1)CtiN—NH_(x)+WF₆→C_(p)H_(q−1)CTiN_(x−1)—WF₅+HF

EXAMPLE 19 ALD Deposition of WN_(x) on Perfluorocarbon Polymer (Low-kDielectric Layer)

[0063] H₂/NH₃ remote plasma generates H atoms and NH_(x) radicals thatleach out fluorine from the hydrocarbon. The leached surface is reactedwith TiCl₄ and followed by TiN or Ti/TiN ALD of a thin intermediatelayer. The NH_(x) terminated surface that is prepared during the TiN ALDis reacted with WF₆ to initiate WN_(x) ALD.

C_(m)F_(n)+H.+NH_(x).→C_(p)F_(q)C.+HF

C_(p)F_(q)C.+TiCl₄→C_(p)F_(q)C—TiN—NH_(x)

C_(p)F_(q)C—TiN—NH_(x)+WF₆→C_(p)F_(q)C—TiNH_(x−1)—NWF₅+HF

EXAMPLE 20 ALD Deposition of Oxide on Another Oxide

[0064] The surface of the first oxide is activated by O₂/H₂/H₂O remoteplasma that includes different ratios of the constituents. This processis used to terminate the surface with OH species that are reactive witha metal precursor for the next oxide layer.

M1O_(x)+O.+H.+OH.→M1O_(x)—OH

M1O_(x)—OH+M2L_(y)→M1O_(x)—O—M2L_(y−1)+HL

EXAMPLE 21 ALD Deposition of Oxide on Metal, Semiconductor or MetalNitride

[0065] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species that are reactive with a metal precursor for initiating ALD.

M1+H.+NH_(x).→M1—NH_(x)

M1NH_(x)+M2L_(y)→M1NH_(x−1)M2L_(y−1)+HL

EXAMPLE 22 ALD Deposition of Metal, Semiconductor or ConductiveMetalnitride on Oxide

[0066] NH₃/H₂/N₂ plasma is used to terminate the surface with NH_(x)species or O₂/H₂/H₂O plasma generated radicals are used to terminate thesurface with OH species. The species are reactive with a metal precursorfor initiating ALD.

M1O_(x)+O.+H.+OH.→M1O_(x)—OH

M1O_(x)—OH+M2L_(y)→M1O_(x)—O—M2L_(y−1)+HL

[0067] Again, it is appreciated that the above are described as examplesonly and that many other ALD reactions and pretreatment procedures areavailable.

[0068] Referring to FIG. 11, an apparatus for practicing the presentinvention is shown. An ALD reactor apparatus 30 is shown as oneembodiment. It is appreciated that a variety of other devices andequipment can be utilized to practice the invention. Reactor 30 includesa processing chamber 31 for housing a wafer 32. The wafer 32 comprisesthe substrate 20 described in the earlier Figures. Typically, the wafer32 resides atop a support (or chuck) 33. A heater 34 is also coupled tothe chuck to heat the chuck 33 and the wafer 32 for plasma deposition.The processing gases are introduced into the chamber 31 through a gasdistributor 35 located at one end of the chamber 31. A vacuum pump 36and a throttling valve 37 are located at the opposite end to draw andregulate the gas flow across the wafer surface.

[0069] A mixing manifold 38 is used to mix the various processing gasesand the mixed gases are directed to a plasma forming zone 39 for formingthe plasma. A variety of CVD techniques for combining gases and formingplasma can be utilized, including adapting techniques known in the art.The remotely formed plasma is then fed into gas distributor 35 and theninto the chamber 31.

[0070] The mixing manifold 38 has two inlets for the introduction ofgases and chemicals. A carrier gas is introduced and the flow split atthe mixing manifold 38. The carrier gas is typically an inert gas, suchas nitrogen. The mixing manifold 38 also has two inlets for thechemicals. In the example diagram of FIG. 11, chemical A and chemical Bare shown combined with the carrier gas. Chemistry A pertains to thefirst precursor and chemistry B pertains to the second precursor forperforming ALD for the two precursor process described above. Chemicalselection manifold 40 and 41, comprised of a number of regulated valves,provide for the selecting of chemicals that can be used as precursors Aand B, respectively. Inlet valves 42 and 43 respectively regulate theintroduction of the precursor chemistries A and B into the mixingmanifold 38.

[0071] The operation of the reactor for performing ALD is as follows.Once the wafer is resident within the processing chamber 31, the chamberenvironment is brought up to meet desired parameters. For example,raising the temperature of the wafer in order to perform ALD. The flowof carrier gas is turned on so that there is a constant regulated flowof the carrier gas as the gas is drawn by the vacuum created by the pump36. When ALD is to be performed, valve 42 is opened to allow the firstprecursor to be introduced into the carrier gas flow. After apreselected time, valve 42 is closed and the carrier gas purges anyremaining reactive species. Then, valve 43 is opened to introduce thesecond precursor into the carrier gas flow. Again after anotherpreselected time, the valve 43 is closed and the carrier gas purges thereactive species form the chambers of the reactor. The two chemicals Aand B are alternately introduced into the carrier flow stream to performthe ALD cycle to deposit a film layer.

[0072] When the pretreatment of the surface is to be performed byplasma, the pretreating species can be introduced into the mixingmanifold through either or both of the chemical selection routes throughselection manifold(s) 40, 41 to mix with the carrier gas. Again, thepretreatment is performed prior to the initial introduction of the firstALD precursor used to deposit the film. Accordingly, the introduction ofthe pretreatment chemistry can be achieved from adapting designs of astandard ALD reactor.

[0073] Thus, an apparatus and method to achieve continuous interface andultrathin film during atomic layer deposition is described. The presentinvention allows an ALD process to start continuously without nucleationor incubation and allows ultrathin film layers of 50 angstroms or lessin thickness to be deposited having continuous uniformity and/orconformity.

We claim:
 1. A method of performing atomic layer deposition comprising:pretreating a surface of a substrate to make the surface of thesubstrate reactive for performing atomic layer deposition; introducing afirst precursor to deposit a first reactive species on the surface ofthe substrate, the pretreated surface being more receptive to havingchemical termination sites for depositing the first reactive species,due to said pretreating the surface; and introducing a second precursorto have a second reactive species react with the deposited firstreactive species.
 2. The method of claim 1 further including forming auniform film layer of 50 angstroms or less in thickness.
 3. The methodof claim 1 wherein said pretreating is performed by a plasma process. 4.The method of claim 1 wherein said pretreating the surface includesintroducing a radical species to attach to the surface of the substrateto increase termination sites for the first reactive species.
 5. Themethod of claim 4 wherein said pretreating is performed by a plasmaprocess.
 6. The method of claim 1 wherein said pretreating the surfaceincludes introducing a radical species to exchange bonds at the surfaceof the substrate to increase termination sites for the first reactivespecies.
 7. The method of claim 6 wherein said pretreating is performedby a plasma process.
 8. The method of claim 1 wherein said pretreatingthe surface includes depositing an intermediate layer on the substrateprior to introducing the first precursor, in which the intermediatelayer provides more termination sites for the first reactive speciesthan the substrate or where the substrate cannot be made reactive toatomic layer deposition.
 9. The method of claim 8 wherein saidpretreating is performed by a plasma process.
 10. The method of claim 8wherein said pretreating is performed by an atomic layer depositionplasma process.
 11. The method of claim 1 wherein said pretreating thesurface includes introducing a radical species to leach molecules fromthe substrate to increase termination sites for the first reactivespecies.
 12. The method of claim 11 wherein said pretreating isperformed by a plasma process.
 13. The method of claim 1 wherein Al₂O₃is deposited on silicon by atomic layer deposition in which saidpretreating includes introducing O₂/H₂/H₂O/NH₃ plasma to form a layer ofsilicon oxide or silicon oxinitride, in which OH or NH_(x) group formsthe chemical termination sites on silicon.
 14. The method of claim 1wherein Al₂O₃ is deposited on silicon by atomic layer deposition inwhich said pretreating includes forming a layer of SiO₂ that ishydroxilated by exposing HF cleaned silicon to a pulse of H₂O to formthe chemical termination sites on silicon.
 15. The method of claim 1wherein Al₂O₃ is deposited on WN_(x) by atomic layer deposition in whichsaid pretreating includes introducing NH₃/H₂/N₂ plasma to leach fluorinefrom WN_(x) to form NH_(x) as the chemical termination sites on WN_(x).16. The method of claim 1 wherein Al₂O₃ is deposited on TiN by atomiclayer deposition in which said pretreating includes introducingNH₃/H₂/N₂ plasma to form NH_(x) as the chemical termination sites onTiN.
 17. The method of claim 1 wherein Al₂O₃ is deposited on Ti byatomic layer deposition in which said pretreating includes introducingNH₃/H₂/N₂ plasma to nitridize the surface to form NH_(x) as the chemicaltermination sites on Ti.
 18. The method of claim 1 wherein Al₂O₃ isdeposited on W by atomic layer deposition in which said pretreatingincludes introducing NH₃/H₂/N₂ plasma to nitridize the surface to formNH_(x) as the chemical termination sites on W.
 19. The method of claim 1wherein Al₂O₃ is deposited on Ta by atomic layer deposition in whichsaid pretreating includes introducing NH₃/H₂/N₂ plasma to nitridize thesurface to form NH_(x) as the chemical termination sites on Ta.
 20. Themethod of claim 1 wherein Al₂O₃ is deposited on Ta_(x)N by atomic layerdeposition in which said pretreating includes introducing NH₃/H₂/N₂plasma to form NH_(x) as the chemical termination sites on Ta_(x)N. 21.The method of claim 1 wherein Ta₂O₅ is deposited on Al₂O₃ by atomiclayer deposition in which said pretreating includes introducingO₂/H₂/H₂O plasma to form OH species as the chemical termination sites onAl₂O₃.
 22. The method of claim 1 wherein Al₂O₃ is deposited on Ta₂O₅ byatomic layer deposition in which said pretreating includes introducingO₂/H₂/H₂O plasma to form OH species as the chemical termination sites onTa₂O₅.
 23. The method of claim 1 wherein TiO_(x) is deposited on Al₂O₃by atomic layer deposition in which said pretreating includesintroducing O₂/H₂/H₂O plasma to form OH species as the chemicaltermination sites on Al₂O₃
 24. The method of claim 1 wherein Al₂O₃ isdeposited on TiO_(x) by atomic layer deposition in which saidpretreating includes introducing O₂/H₂/H₂O plasma to form OH species asthe chemical termination sites on TiO_(x).
 25. The method of claim 1wherein TiO_(x) is deposited on TiN by atomic layer deposition in whichsaid pretreating includes introducing NH₃/H₂/N₂ plasma to form NH_(x)species as the chemical termination sites on TiN.
 26. The method ofclaim 1 wherein W is deposited on TiN by atomic layer deposition inwhich said pretreating includes introducing NH₃/H₂/N₂ plasma to formNH_(x) species as the chemical termination sites on TiN.
 27. The methodof claim 1 wherein WN_(x) is deposited on TiN by atomic layer depositionin which said pretreating includes introducing NH₃/H₂/N₂ plasma to formNH_(x) species as the chemical termination sites on TiN.
 28. The methodof claim 1 wherein WN_(x) is deposited on SiO₂ by atomic layerdeposition in which said pretreating includes introducing O₂/H₂/H₂Oplasma to form OH species that are reactive with TiCl₄ and in which theTiCl₄ is used to grow an intermediate layer of Ti or TiN to form NH_(x)as the chemical termination sites on Ti or TiN.
 29. The method of claim1 wherein W is deposited on SiO₂ by atomic layer deposition in whichsaid pretreating includes introducing O₂/H₂/H₂O plasma to form OHspecies that are reactive with TiCl₄ and in which the TiCl₄ is used togrow an intermediate layer of Ti or TiN to form NH_(x) as the chemicaltermination sites on Ti or TiN.
 30. The method of claim 1 wherein W isdeposited on SiO₂ by atomic layer deposition in which said pretreatingincludes introducing O₂/H₂/H₂O plasma to form OH species that arereactive with TaCl₅ and in which the TaCl₅ is used to grow anintermediate layer of Ta_(x)N to form NH_(x) as the chemical terminationsites on Ta_(x)N.
 31. The method of claim 1 wherein WN_(x) is depositedon hydrocarbon polymer by atomic layer deposition in which saidpretreating includes introducing NF₃ plasma to generate fluorine atomsthat leach hydrogen from the hydrocarbon polymer and in which theleached surface is reacted with TiCl₄ to grow an intermediate layer ofTiN or a combination of Ti/TiN to form NH_(x) as the chemicaltermination sites on TiN or Ti/TiN.
 32. The method of claim 1 whereinWN_(x) is deposited on perfluorocarbon polymer by atomic layerdeposition in which said pretreating includes introducing H₂/NH₃ plasmato generate hydrogen atoms and NH_(x) radicals that leach fluorine fromthe hydrocarbon polymer and in which the leached surface is reacted withTiCl₄ to grow an intermediate layer of TiN or a combination of Ti/TiN toform NH_(x) as the chemical termination sites on TiN or Ti/TiN.
 33. Themethod of claim 1 wherein a second oxide is deposited on a first oxideby atomic layer deposition in which said pretreating includesintroducing O₂/H₂/H₂O plasma to activate the first oxide and toterminate the surface with OH species that are reactive with a metalprecursor for the second oxide layer.
 34. The method of claim 1 whereinan oxide is deposited on metal, semiconductor or metal nitride by atomiclayer deposition in which said pretreating includes introducingNH₃/H₂/N₂ plasma to terminate the surface with NH_(x) species that arereactive with a metal precursor.
 35. The method of claim 1 wherein ametal, semiconductor or conductive metalnitride is deposited on oxide byatomic layer deposition in which said pretreating includes introducingNH₃/H₂/N₂ plasma which is used to terminate the surface with NH_(x)species.
 36. The method of claim 1 wherein a metal, semiconductor orconductive metalnitride is deposited on oxide by atomic layer depositionin which said pretreating includes introducing O₂/H₂/H₂O plasmagenerated radicals which are used to terminate the surface with OHspecies.
 37. An apparatus for performing atomic layer depositioncomprising: a processing chamber for subjecting a substrate to atomiclayer deposition to deposit a film layer; a mixing manifold for mixingchemicals with a carrier gas, said mixing manifold coupled to saidprocessing chamber for delivery of a first precursor chemical during afirst time period and delivery of a second precursor chemical during asecond period to generate a first and second plasma, respectively, toperform atomic layer deposition to deposit the film layer; said mixingmanifold also coupled to receive a pretreating chemical specie forcoupling into said processing chamber prior to introduction of the firstand second precursor chemicals, said pretreating chemical specieintroduced into said processing chamber to pretreat the substratesurface to make its surface more reactive to the first precursorchemical.
 38. The apparatus of claim 37 wherein said pretreatingchemical specie introduces a radical species to attach to the surface ofthe substrate to increase termination sites for the first precursorchemical.
 39. The apparatus of claim 37 wherein said pretreatingchemical specie introduces a radical species to exchange bonds at thesurface of the substrate to increase termination sites for the firstprecursor chemical.
 40. The apparatus of claim 37 wherein saidpretreating chemical specie deposits an intermediate layer on thesubstrate prior to introducing the first precursor chemical, in whichthe intermediate layer provides more termination sites for the firstprecursor chemical or where the substrate cannot be made reactive toatomic layer deposition.
 41. The apparatus of claim 37 wherein saidpretreating chemical specie introduces a radical species to leachmolecules from the substrate to increase termination sites for the firstprecursor chemical.
 42. A method to perform atomic layer depositioncomprising: pretreating a surface of a substrate or a material layerformed on the substrate by introducing a radical specie including anycombination of O₂, H₂, H₂O, NH₃, NF₃, N₂, Cl and F to increase AH_(x)termination sites on the surface, where x is an integer and A is anon-metal capable of bonding with hydrogen H; introducing a firstprecursor to deposit a first reactive specie on the surface, the surfacewhen pretreated being more receptive to have additional bonding with thefirst reactive specie, due to the increase of AH_(x) termination siteson the surface; and introducing a second precursor, after the bonding ofthe first reactive specie, to deposit a second reactive specie to reactwith the deposited first reactive specie to form a film layer.
 43. Themethod of claim 42 further including forming the film layer to have athickness of 50 angstroms or less by repeatedly introducing the firstprecursor followed by the second precursor.
 44. The method of claim 42wherein said pretreating the surface includes introducing the radicalspecie to exchange bonds at the surface of the substrate to increaseAH_(x) termination sites for the first reactive specie.
 45. The methodof claim 42 wherein said pretreating the surface forms NH_(x)termination sites.
 46. The method of claim 42 further comprising formingan intermediate layer on the substrate prior to introducing the firstprecursor, wherein the radical specie is introduced with theintermediate layer to increase termination sites for the first reactivespecie.
 47. The method of claim 42 wherein said pretreating the surfaceincludes introducing the radical specie to leach molecules from thesubstrate to increase termination sites for the first reactive specie.48. The method of claim 42 wherein said pretreating further includesintroducing the radical specie by plasma.
 49. The method of claim 42wherein said pretreating further includes introducing the radical specieby plasma and the reactive species form the film layer, wherein the filmlayer is comprised of a metal, metal oxide or metal nitride.
 50. Themethod of claim 48 wherein Al₂O₃ is deposited on silicon by atomic layerdeposition in which said pretreating includes introducing O₂/H₂/H₂O/NH₃plasma to form a film layer of silicon oxide or silicon oxinitride, inwhich OH or NH_(x) group forms the termination sites on silicon.
 51. Themethod of claim 48 wherein Al₂O₃ is deposited on WN_(y), where y is aninteger, by atomic layer deposition in which said pretreating includesintroducing NH₃/H₂/N₂ plasma to leach fluorine from WN_(y) to formNH_(x) as the termination sites on WN_(y).
 52. The method of claim 48wherein Al₂O₃ is deposited on TiN by atomic layer deposition in whichsaid pretreating includes introducing NH₃/H₂/N₂ plasma to form NH_(x) asthe termination sites on TiN.
 53. The method of claim 48 wherein Al₂O₃is deposited on Ti by atomic layer deposition in which said pretreatingincludes introducing NH₃/H₂/N₂ plasma to nitridize the surface to formNH_(x) as the termination sites on Ti.
 54. The method of claim 48wherein Al₂O₃ is deposited on W by atomic layer deposition in which saidpretreating includes introducing NH₃/H₂/N₂ plasma to nitridize thesurface to form NH_(x) as the termination sites on W.
 55. The method ofclaim 48 wherein Al₂O₃ is deposited on Ta by atomic layer deposition inwhich said pretreating includes introducing NH₃/H₂/N₂ plasma tonitridize the surface to form NH_(x) as the termination sites on Ta. 56.The method of claim 48 wherein Al₂O₃ is deposited on Ta_(y)N, where y isan integer, by atomic layer deposition in which said pretreatingincludes introducing NH₃/H₂/N₂ plasma to form NH_(x) as the terminationsites on Ta_(y)N.
 57. The method of claim 48 wherein Ta₂O₅ is depositedon Al₂O₃ by atomic layer deposition in which said pretreating includesintroducing O₂/H₂/H₂O plasma to form OH specie as the termination siteson Al₂O₃.
 58. The method of claim 48 wherein Al₂O₃ is deposited on Ta₂O₅by atomic layer deposition in which said pretreating includesintroducing O₂/H₂/H₂O plasma to form OH specie as the termination siteson Ta₂O₅.
 59. The method of claim 48 wherein TiO_(z), where z is aninteger, is deposited on Al₂O₃ by atomic layer deposition in which saidpretreating includes introducing O₂/H₂/H₂O plasma to form OH specie asthe termination sites on Al₂O₃
 60. The method of claim 48 wherein Al₂O₃is deposited on TiO_(z), where z is an integer, by atomic layerdeposition in which said pretreating includes introducing O₂/H₂/H₂Oplasma to form OH specie as the termination sites on TiO_(z).
 61. Themethod of claim 48 wherein TiO_(z), where z is an integer, is depositedon TiN by atomic layer deposition in which said pretreating includesintroducing NH₃/H₂/N₂ plasma to form NH_(x) specie as the terminationsites on TiN.
 62. The method of claim 48 wherein W is deposited on TiNby atomic layer deposition in which said pretreating includesintroducing NH₃/H₂/N₂ plasma to form NH_(x) specie as the terminationsites on TiN.
 63. The method of claim 48 wherein WN_(y), where y is aninteger, is deposited on TiN by atomic layer deposition in which saidpretreating includes introducing NH₃/H₂/N₂ plasma to form NH_(x) specieas the termination sites on TiN.
 64. The method of claim 48 whereinWN_(y), where y is an integer, is deposited on SiO₂ by atomic layerdeposition in which said pretreating includes introducing O₂/H₂/H₂Oplasma to form OH specie that are reactive with TiCl₄ and in which theTiCl₄ is used to grow an intermediate layer of Ti or TiN to form NH, asthe termination sites on Ti or TiN.
 65. The method of claim 48 wherein Wis deposited on SiO₂ by atomic layer deposition in which saidpretreating includes introducing O₂/H₂/H₂O plasma to form OH specie thatare reactive with TiCl₄ and in which the TiCl₄ is used to grow anintermediate layer of Ti or TiN to form NH_(x) as the termination siteson Ti or TiN.
 66. The method of claim 48 wherein W is deposited on SiO₂by atomic layer deposition in which said pretreating includesintroducing O₂/H₂/H₂O plasma to form OH specie that is reactive withTaCl₅ and in which the TaCl₅ is used to grow an intermediate layer ofTa_(z)N, where z is an integer, to form NH_(x) as the termination siteson Ta_(z)N.
 67. The method of claim 48 wherein WN_(y), where y is aninteger, is deposited on hydrocarbon polymer by atomic layer depositionin which said pretreating includes introducing NF₃ plasma to generatefluorine atoms that leach hydrogen from the hydrocarbon polymer and inwhich the leached surface is reacted with TiCl₄ to grow an intermediatelayer of TiN or a combination of Ti/TiN to form NH_(x) as thetermination sites on TiN or Ti/TiN.
 68. The method of claim 48 whereinWN_(y), where y is an integer, is deposited on perfluorocarbon polymerby atomic layer deposition in which said pretreating includesintroducing H₂/NH₃ plasma to generate hydrogen atoms and NH_(x) radicalsthat leach fluorine from the hydrocarbon polymer and in which theleached surface is reacted with TiCl₄ to grow an intermediate layer ofTiN or a combination of Ti/TiN to form NH_(x) as the termination siteson TiN or Ti/TiN.
 69. The method of claim 48 wherein an oxide isdeposited on metal, semiconductor or metal nitride by atomic layerdeposition in which said pretreating includes introducing NH₃/H₂/N₂plasma to terminate the surface with NH_(x) specie that are reactivewith a metal precursor.
 70. The method of claim 48 wherein a metal,semiconductor or conductive metal nitride is deposited as the film layeron oxide by atomic layer deposition in which said pretreating includesintroducing NH₃/H₂/N₂ plasma which is used to terminate the surface withNH_(x) specie.
 71. A method to perform atomic layer depositioncomprising: depositing an intermediate layer; pretreating a surface ofthe deposited intermediate layer by introducing a radical specieincluding any combination of O₂, H₂, H₂O, NH₃, NF₃, N₂, Cl and F toincrease AH_(x) termination sites on the surface, where x is an integerand A is a non-metal capable of bonding with hydrogen H; introducing afirst precursor to deposit a first reactive specie on the surface, thesurface when pretreated being more receptive to have additional bondingwith the first reactive specie, due to the increase of AH_(x)termination sites on the surface; and introducing a second precursor,after the bonding of the first reactive specie, to deposit a secondreactive specie to react with the deposited first reactive specie toform a film layer.
 72. A method to perform atomic layer depositioncomprising: leaching hydrogen or fluorine from a surface by pretreatingthe surface by introducing a radical specie including any combination ofO₂, H₂, H₂O, NH₃, NF₃, N₂, Cl and F to increase AH_(x) termination siteson the surface, where x is an integer and A is a non-metal capable ofbonding with hydrogen H; introducing a first precursor to deposit afirst reactive specie on the surface, the surface when pretreated beingmore receptive to have additional bonding with the first reactivespecie, due to the increase of AH_(x) termination sites on the surface;and introducing a second precursor, after the bonding of the firstreactive specie, to deposit a second reactive specie to react with thedeposited first reactive specie to form a film layer.
 73. A structureformed on a substrate comprising: a material layer formed on thesubstrate in which the material layer is pretreated by introducing aradical specie including any combination of O₂, H₂, H₂O, NH₃, NF₃, N₂,Cl and F to increase AH_(x) termination sites on the surface of thematerial layer, where x is an integer and A is a non-metal capable ofbonding with hydrogen H; a film layer formed above said material layerby repeated introduction of a first precursor followed by a secondprecursor to deposit said film layer by atomic layer deposition, thefirst precursor to deposit a first reactive specie on the surface of thematerial layer, the surface when pretreated being more receptive to haveadditional bonding with the first reactive specie, due to the increaseof AH_(x) termination sites on the surface and the second precursor todeposit a second reactive specie to react with the deposited firstreactive specie to form said film layer.